Herbicidal composition and method



including both broadleaf and grass-weeds.

3,185,561. I HERBICIDAL COMPOSITION AND METHOD Donald S. A'cker,Waynesboro, Va., assignor to E; I.

du Pont de Nemoursand Company, Wilmington, Del.,

a corporation of Delaware No Drawing. Filed Apr. 9 1962, Ser. No.185,849 3 Claims. (Cl. 71--2.5) p X This application is acontinuation-in-pait of my application Serial No. 846,062, filed'October13,1959, which is a continuation-impart of my application Serial No.679,760, filedAugust 22, 1957, and both now abandoned.

This invention relates to a certain class of novel-substitutedsymmetrical triazines.

This class of triazines is represented by the formula United StatesPatent 0 3,185,561 Patented May 25, 1965 ice amines in three. steps. Onechlorine atom is replaced at 0 C., the second at 3050 C., and the thirdat 90 100C. (Fries, Ber. 19, 242, 2055 (1886)). Thus, one equivalent ofa given alkoxyalkyl amine reacted with cyanuric chloride at 0 C. yieldsthecorresponding 2,4-

. dichloro-6-(alkoxyalkylamino) triazine. Such compounds can be reactedfurther at -40 C. with another equivalent alkoxyalkylamine and then withan equivalent of a metal alkoxide or mercaptide at reflux temperature toyield the compounds of this invention as illustrated by Equation 2above.

The compounds of this invention are solids or oils which are relativelyinsoluble in water. Thecompounds illustrated by Equation 2 above aregenerally oils or low melting solids and are soluble in kerosene,xylene, alcohol and benzene.

From a standpoint of herbicidal activity and ease and economy ofpreparation,among the best compounds of the present invention are thosewherein Y is an alkoxy radical, and preferably methoxy and n equals 3.These compounds give perhaps the quickest weed control-of all n is awhole positive integer from 3 through 8, preterably 3; l

m is a whole positive integer from 1 through 8; and

Y is a member of the group consisting of OR and SR where R is an alkylgroupbt less than 3 carbon atoms.

These novel substiuted triazines can be prepared by reacting analkoxyalkylamino substituted symmetrical triazine with a metal alkoxideor mercaptide in an alcohol solvent as described by Equation 2.

N N NaOR or NaSR wherein R is the same as defined above. p

The novel triazine reactant shown in Equation 2 above and the other2-chloro-4,6-di(alkoxyalkylamino)s-tria- Zines used to prepare somecompounds of this invention can be prepared conveniently bythereactionof cyanuric chloride with two mol equivalents of3-methoxypropylamine, 2-amino-l methoxypropane orisimilar alkoxyalkylamines. a .It is well known that cyanuriglch loride reacts with thecompounds represented by Formula 1, insofar as postemergence herbicidalactivity is concerned.

Particularly preferred because of its excellent control .of plants atlow rates is: 2-methylmercapto-4,6*bis-(3-methoxypropylamine)-s-triazine.

In .use these compounds can be applied to areas to be protected fromundesirable vegetation in any of a variety of compositions. soluble canbe applied simply as water solutions.

It is preferred, however, that the compounds be ex-i tended with carriermaterials or conditioning agents of the kind used and referred to in theart as herbicidal adju vants or modifiers. Inert solids, surface-activeagents, and organic liquids are examples of such adjuvants.

The compounds shown above will be included in any compositions insufiicient amount to. exert a herbicidal .compound with a suitableliquid diluent.

efiect, usually from about 0.5% to by weight.

.. Power formulations can be prepared withinert solids.

The formulations thus can be prepared with insert solids to form dusts.The powders usually comprise the active ingredient admixed with minoramounts of conditioningagent. Natural clays (either. absorptive, such asattapulgite, or relatively nonabsorptive, such as china clays),diatoma'ceous earth, walnut shell flour, redwood flour, synthetic finesilica, calcium silicate, and'other inert solid carriers of the kindconventionally employed in powder herbicidal compositions can be used.The active ingredient usually makes up from about 20-75% of these powdercompositions. The solids ordinarily should be very finely divided andshould have a particle size below about 50 microns and preferably belowabout 20 microns. Talc, pyrophyllite, tobacco dust, volcanic ash, andother dense rapid-settling insert solids customarily are used forconversion of the powders to dusts.

l The active compound, either alone or with other conditioning agents,may be dissolved or dispersed in Water and then sprayed, or in any otherdesired manner, applied to an absorptive powder or granule, which canthen be dried to produce a dry product. It can also be mixed withsufficient water to form a paste which can be extruded in pellet form.Any of the above absorptive materials can be used for the preparation ofsuch products.

Liquid compositions including the active compounds abovedescri-bed. canbe prepared by admixing the active The active compound can be either insolution or in suspension.

-Typical of the liquid media commonly employed are kerosene, Stoddardsolvent, xylene, alcohols, alkylated naphthalene, diesel oil, glycolsand ketones such as diisobutyl ketone, .cyclohexanone, etc. The activeingredient Thus any that are sufiiciently Wateru usually makes up fromabout 0.5 to 50% of these liquid compositions. Some of thesecompositions are designed to be used as such, and other are to beextended with large quantities of water or with other organic solvents.

per acre of the active ingredient. Under some conditions, rates as lowas 20 pounds per acre will give satisfactory control of vegetation.Application at rates of about 0.5 to pounds per acre of the activeingredient for pre- Compositions in the form of wettable powders or liq-5 emergence or early directed post-emergence treatment uids can alsoinclude one or more surface-active agents gives excellent control ofbroadleaf weeds and grasses in such as wetting, dispersing, oremulsifying agents. Thus in hardy crop plants such as corn, sorghum,sugar cane, mixtures of the above liquids with the active compounds andcotton. can contain an emulsifying agent to make an emulsifiable Inorder that the invention can be better understood, oil composition. Thesurface-active agents cause the comthe following examples are given inaddition to those set positions to disperse or emulsify easily in waterto give forth above: aqueous sprays. EXAMPLE 1 sgg g i 'ii gz giig f tgl gif g s; To a solution of 29.7 parts of sodium methoxide in 800 yp y 3parts of methanol is added 145 parts of 2,4-bis(3-methoxyample, sodiumoleate, sulfonated petroleum OllS, alkyl m hmino) 6 chlom s triazine Themixture is aryl sulfonates, sodium lauryl sulfate, polyethylene oxides,S 2? about fiva hours allo'wed to cool and filtered and ligninsulfonates. A detailed list of such agents 15 frogn the odium chioridefiltr t6 o bined with set forth in an article by McCutcheon in Soap andChem- 500 f t ti i c e t t d ical Specialties, volume 31, Nos. 7-10(1955), and more 82; fi g recently in the booklet by John W. McCutcheon,Inc., 20 1 1 a 0 Par S W612 i Detergents and Emu1sifierS Up to Date,1960 y ene c on e. 1 e methylene chloride solution, drie Generally,surfactants will be present in the range of Over Mgs04 filteled andSmpped solvent'free under 0.5 to 10% by weight. However, surfactants canbe duced Pressure yields essennilny pure product namely used with thecompounds of this invention at much higher bls T' 6 methoxy s levels toincrease the biological action of the active com- 1D pounds. It is foundthat many surfactants, when used in an amount equal to that of theherbicide, or in even EXAMPLES 2 8 greater amounts up to 3 to 10 timesthe weight of herbi- The products listed in the following table areprepared cide produce a greatly enhanced activity, causing high inaccordance with the procedure of Example 1 by replacherbicidaleffectiveness at very low herbicide use rates. ing the chlorotriazineand alkoxide of Example 1 with The most highly effective surfactants arethe non-ionic the reagents listed in Table I.

Table I Chlorotrinzine Parts used Alkoxide Parts used Product obtained2-chloro-4,6-bis-(3-ethoxypr0pyl- 125.5 Sodium ethoxide 74.82-eth0xy-4,6-bis-(B-ethoxypropylamino)-s-triazine. amino)-s-triazine.2-ehloro-4,6-bis-(3-methcxypropyl- 118.5 Sodium methyl mercaptide. 772-methylmcreapto-4,6-bis-(3-mcthamino)striazine.oxypropylamino)-s-triazine. 2,4-bis(3-propoxypropylamiuo)-6- 159Sodiumethoxide 37.4 2,4-bi's(3-propoxypropylamino)-6- chloro-s-triazine.ethoxy-s-triazine. 2,4-bis(3-methoxypropylamino)-6 145 Sodium ethylmercaptide 46.2 2,4-bis(3-methoxypropy1a1nino)-6- chloro-s-triazine.ethyl-mercapto-s-triazine. 2,4-bis(3-ethoxypropylamino)-6- 152 Sodiummethoxide 29.7 2,4 bis(B-ethoxypropylamino)-G- ehloro-s-triazine.methoxy-s-triazine. 2,4-bis[3-(1-octyl)-oxypropylam- 243.5 -.d0 29.72,4-bis[3-(1-oetyl)oxypropylamino]-6-chloro-s-triazine.ino]-6-methoxy-s-triazinc. 2,4-bis(4-methoxybutylamin0)-6- 159 ..do 29.72,4-bis(4-methoxybutylamino)-6- chloro-s-triazine. methoxy-s-triazine.

members which are polyethylene oxide adducts of long chain alcohols orfatty acid glycerol, sorbitan or other polyglycol esters. A number ofanionic sulfonates or sulfates are also active such as sodiumdodecylbenzenesulfonate or sodium lauryl sulfate.

The compounds can be applied in compositions of the types shown in JonesUS. Patent 2,412,510 in which an active compound of this inventionreplaces the active materials of that patent in the composition shownand in like amount. Similarly, any of the carriers, additives, orsurface-active agents there named or referred to can be used.

The herbicidal method of the present invention comprises applying asubstituted triazine of Formula 1, ordinarily in a herbicidalcomposition of the aforementioned type, to the locus or area to beprotected from undesirable plant growth. The active compound is, ofcourse, applied in sufiicient amount to exert the desired herbicidalaction. The application can be made directly upon the locus or area andthe vegetation thereon during the period of infestation. Alternatively,the application can be made in advance of an anticipated weedinfestation.

The dosage employed can be determined readily by those skilled in theart by conventional techniques. It is, of course, dependent upon theparticular active ingredient employed, the nature of the formulationused, the type of treatment, the type of vegetation to be controlled,climatic conditions, and the like. In general, complete control ofvegetation is obtained at rates of about 40 to 80 pounds The followingcompounds are also prepared in accordance with the procedure of Example1 by utilizing the appropriate starting materials:

EXAMPLE 25 acids concreted with urea 3 Low viscosity methyl cellulose0.5 Disodium phosphate 1.5

High surface area calcium silicate 45 The ingredients are blended and pare passed once through a micropulverizer using no retaining screen.After this initial grinding-mixing step, the product is ground throughthe same micropulverizer using an 0.020 inch round hole screen. Care istaken that the mill does not heat up too much during the grinding step.If desired, cooling agents such as Dry Ice may be ground along with theproduct. After grinding the product has a particle size of less than 50microns.

The resulting composition, when applied at a rate of 40 pounds per acreof active ingredient in .200 gallons of water, gives rapid kill offoliage of ragweed, rough pigweed, yellow foxtai-l, mustard, and crabgrass. Outstanding weed control is noted for an extended periodbf time.

Another portion of this formulation is applied at a rate of 4 pounds ofactive ingredient per acre in 80 gallons of Water as a pre-ernergencetreatment to fields planted to corn and sugar cane. Excellent control ofannual broadleaf and grass weeds is obtained.

The ingredients are blended by simple stirring; the materials are heatedgently to approximately 5060 C. in order to facilitate the mixing. i p

The product is an emulsifiable oil that can be extended with water toform emulsions that are suitable for spraying. Alternatively, the oilconcentrate can be extended with otherorganic solvents, such as dieseloil.

This product, When applied at a rate of 80 pounds of active ingredientper acre after extension with waterto Percent make a total applicationof 250 gallons of solution per acre, gives excellent control of a mixedinfestation ofgrass and broadleaf weeds along fence rows. Anfapplicationof 25 pounds (active) per acre gives control of annual weeds growingaround signposts.

EXAMPLE 27 A dust composition is prepared as follows i i i t i i Percent2-ethoxy-4,6-bis(3-ethoxypropylamino)-s-triazine 10 High surface areafine silica 20 Walnut shell flour 70 twicethrough a micropulverizerinorder to mix the tri-azine with the silica and reduce its particlesize. After grinding the mixture is incorporated into thewalnut shellflour to yield a dust suited for dustapplication of the herbicide inconventional equipment.

This composition is applied with a hand duster at the rate of 800 poundsper acre to weed infested areas around the base of telephone poles.Excellent control of crab grass, yellow foxtail, jimson weed, poke weed,and ragweed is noted.

6 EXAMPLE 2:;

The following oil composition is prepared:

Percent p The ingredients are mixed and stirred until homogeneous, thisis facilitated by gentle heating to approximately 80 C.

The resulting product can be extended with aromatic oils or diesel oil;this product, however, cannot be diluted with water.

This composition is applied at the rate of 60 pounds per acre of activeingredient after extension with 200 gallons of diesel oil to .a railroadright-of-Way with a specially equipped railroad car. Rapid top-kill offoliage is noted on a mixed infestation of annual and perennialbroadleaf and grass weed-s. Good residual weed control is obtained inthis area.

EXAMPLE 29 i The triazines can also be prepared and applied in granularform as shown:

Percent 2,4-bis(3-propoxypropylamino)-6-ethoxy-s-triazine 2 Granularattapulgite fullers earth (15-30 mesh) 98 Two pounds of2,4-bis(3-propoxypropylamino)-6- ethoxy-s-triazine are heated until thecrystals are molten, and are sprayed on 98 pounds of granularattapulgite fullers earth (15-30 mesh) which is maintained at the sametemperature inside a heated drum blender. Agitation is continued untilthe active ingredient is homogeneously dispersed throughout the mass.The products are then allowedto cool.

This granular formulation is "applied at the rate of 3,000.

pounds per acre by means of a special type of fertilizer distributor.Excellent control of broadleaf and grass weeds growing along highwayguard rails is obtained.

EXAMPLE 30 t 1 Percent2-methoxy-4,6-bis(3-methoxypropylarnino)-s-triazine 2 Granularvermiculite 98 The active, is applied to the vermiculite in molten formas described in Example 29.

This formulation is applied with a tractor-drawn granular spreader atthe rate of 2 pounds (active) per acre for the pre-emergence control ofannual broadleaf and grass weeds in corn. Excellent weed control isobtained.

The ingredients are mixed and are passed three times through themicropulverizer with an 0.020 herringbone screen. a

1 The product'is a finely divided powder with the majority of particlessmaller than 50 microns.

Thiseornposition, when applied at the rate of pounds per acre ofactiveingredient in 300 gallons of water, gives excellent control of annualand perennial weeds growing in Warehouse storage'areas.

7 EXAMPLE 32 The following dust composition is prepared:

Percent 2,4-bis-(3-methoxypropylamino)- 6 methoxy-s-triazine Sodium saltof alkylated naphthalene sulfonic acid 1 Lauryl alcohol 0.5 Micaceoustalc 88.5

The triazine is blended with four times its weight of talc and is groundand deagglomerated in the micropulverizer. If necessary, cooling agentssuch as Dry Ice may be used to keep the grinding temperature inside themicropulverizer sufiiciently low to avoid caking.

This ground product is blended with the other ingrediants and remainingtalc to make a dust composition suitable for use as herbicidal dust.

This dust composition is applied at the rate of 600 pounds per acre witha specially adapted duster to a mowed grass stubble in a warehouse area.Good control of such undesirable grasses as quack grass, crab grass,foxtail, cheat and barnyard grass is obtained.

EXAMPLE 33 In order to form a granular formulation of the triazine, thefollowing wettable powder is first prepared:

Percent 2,4-bis (4-butoxybutylamino 6-methylmercapto-s-triazine 50Sodium dioctyl sulfosuccinate (85%) concreted with The ingredients arecarefully blended and ground by air reductionizing. Two pounds of thewettable powder above is mixed with approximately 97 pounds of granularattapulgite fullers earth (-30 mesh) in a ribbon blender. When the blendis homogeneous, two pounds of a 50:50 weight mixture of water andethylene glycol are sprayed in while the blender ribbons are agitatingthe mixture. Blending and drying of the paste produces a granularproduct which contains approximately 1% of the triazine herbicide.

This 1% formulation, when applied at the rate of 60 pounds per acre ofthe active ingredient, gives excellent control of undesirable vegetationaround highway signs, boundary fences, and safety fences.

EXAMPLE 34 A wettable powder of the following composition is prepared:

The ingredients are blended and are passed once through amicropulverizer using no retaining screen. After this initialgrinding-mixing step, the product is ground through the samemicropulverizer using an 0.020 inch round hole screen. Care is takenthat the mill does not heat up too much during the grinding step; ifdesired, cooling agents such as Dry Ice may be ground along with theproduct. The product after grinding has a particle size of less than 50microns.

The resulting powder can be used by adding it to water in order to formspray suspensions that can be used in conventional spray equipment. Whenapplied at the rate of 80 pounds per acre of active ingredient in 300gallons of water, excellent control is obtained of a wide variety ofannual weeds growing on a tennis court.

EXAMPLE 35 The following oil composition is prepared:

Percent 2 methylmercapto 4,6 bis (S-methoxypropylamino)-s-triazine 50alkylated naphthalenes, largely alpha-methyl naphthalene Polyethyleneoxide esters of mixed resin and fatty acids 8 The ingredients are mixedand stirred together at a slightly elevated temperature to make an oilcomposition which, upon addition to water, forms an emulsion for use asa herbicidal spray. Or, if desired, the 50% oil composition above can beextended with organic solvents such as straight chain hydrocarbons,aromatic oils and diesel oil.

This formulation is applied at the rate of 50 pounds per acre of activeingredient in 150 gallons of diesel oil with a hand-operated pressurespray. This treatment gives excellent control of a mixed population ofgrass and broadleaf weeds under a cyclone boundary fence. Weed species,such as crabgrass, barnyard grass and pigweed are controlled with 20pounds (active) in 80 gallons of 0 diesel oil.

EXAMPLES 36 AND 37 2,4 bis(methoxyisopropylamino) 6-methoxy-s-triazineis substituted for the active ingredient in Examples 25 and 31 in likeamount by weight. The substituted active ingredient is formulated inlike manner. The new composition gives like results when used in thesame manner as the composition of Examples 25 and 31.

EXAMPLE 38 2,4 bis (methoxyisopropylamino) 6-methyln1ercaptos-triazineis substituted for the active ingredient in Ex ample 26 in like amountby weight. The substituted active ingredient is formulated in likemanner. The new composition gives like results when used in the samemanner as the composition of Example 26.

EXAMPLE 39 7 Percent 2 methylmercapto 4,6bis(3-methoxypropylamino)-s-triazine 25.0 Alkyl naphthalene sulfonicacid, Na salt 1.0 Partially desulfonated sodium lignin sulfonate 1.0Attapulgite clay 73.0

The above composition is blended and micropulverized until substantiallyall particles are below 50 microns.

One pound (active) of the above product is mixed with two pounds oftrimethylnonylpolyethylene glycol ether (6 mols ethylene oxide) in 35gallons of water.

This tank mixture has utility for directed postemergence weed control insugar cane, sweet corn and field corn. Thirty-five gallons of this spraymixture is applied to a vigorous growth of annual weeds about 1 /2 to 4inches high, present in corn which has reached a height of 11 to 16inches. The spray is directed on the weeds and at the base of the cornplant. Good control of crabgrass, foxtail, barnyard grass, pigweed,lambs-quarters, and velvet leaf is obtained. The corn shows excellentgrowth.

I claim:

1. A herbicidal composition containing 0.5 to 10% by weight of asurface-active agent, 25 to 80% by weight of a pulverized solid diluentand 20 to by weight of a compound represented by the formula:

9 10 wherein Y is a member of the group consisting of OR and SR R isselected from the group consisting of 22 :3: R 1s an alkyl group of lessthan Carbon -oIanom) 4-1 and FOIL-(CH y I 5 References Cited by theExaminer n is a Whole positive integer from 3 through 8; UNITED STATESPATENTS m is a whole positive integer from 1 through 8; and 2 237 584 4/41 Bruson 26Q 249 8 Y is a member of the group consisting of OR and SR1 1/45 DAlelio 260 249'6 X where R is an alkyl group of less than 3carbon 497,917 2/50 St flf 3 atoms- 10 2,780,623 2/57 Welcher et a1.260-2498 2. A composition according to claim 1, the composi- 2,820,0331/58 Kaiser et a1. 260-2498 tion additionally containing 1 t 5 parts byweight of a 2,891,855 6/59 Gysin et a1. 71-2.5 surface-active agent foreach part of active compound of 2,909,420 10/59 Gysin et a1. 71-2.5claim 1. U 2,909,421 10/59 Gysin et a1. 712.5 3. The method for thecontrol of weeds comprising ap- 3,022,150 2/62 Weed 71-2.5 plying to thelocus to be treated, in a herbicidally ef- 3,037,853 6/62 Luckenbaugh712.5 fective amount, a compound represented by the formula: 3,152,88210/64 Luckenbaugh 712.6 X

' i FOREIGN PATENTS 456,843 5/49 Canada. 1R 1:; 880,433 12/42 France. 1239 783 7/60 France. omHm o- R H-c -NE- R o-OmHm 1 2 H N a 2 222,71911/49 Switzerland. wherein OTHER REFERENCES R1 is selected from thegroup consisting of Koopman: Nieuwe Herbicide 1,3,5-TriazineDerivaaHdVPCHAOHQWP] ten, May 31, 1957, pages 58 to 62. H3 LEWES GO'ITS,Primary Examiner. n is a whole positive integer from 3 through 8; RV MARCUS BRINDISI, Examiners m is a whole positive integer from 1, through8; and

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No,3,185,561 May 25, 1965 Donald S. Acker It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected below.

Column 2, line 39, for "Power" read Powder lines 3 40 and S4 for"insert", each occurrence, read inert column 5, line 3, for other" readothers column 4, line 7, strike out "in"; column 6, lines 7 and 8, for"homogeneous," read homogeneous; column 8, lines 70 to 75, for thatportion of the formula reading (R )=Nllread (R dilicolumn 10, line 8,for "D'Alelio Z60-249.6 X" read DAlelio 260-249. 6 XR Signed and sealedthis 12th day of October 1965.

(SEAL) Attest:

ERNEST fw'. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A HERBICIDAL COMPOSITION CONTAINING 0.5 TO 10% BY WEIGHT OF ASURFACE-ACTIVE AGENT, 25 TO 80% BY WEIGHT OF A PULVERIZED SOLID DILUENTAND 20 TO 75% BY WEIGHT OF A COMPOUND REPRESENTED BY THE FORMULA: